Detergent compositions containing sulfonylphenol compounds



'No Drawing.

gree of adsorption upon treated fabrics.

United States Patent 3,249,549 DETERGENT COMPOSITIONS CONTAINING SULFONYLPHENOL COMPOUNDS John Hodge Markgraf, Williamstown, Mass., and Edward Curtis Taylor, Princeton, N.J., assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio Original application May 7, 1962, Ser. No. 193,006. Divided and this application June 2, 1965, Ser. No. 476,224

3 Claims. (CL 252-138) This application is a division of'copending patent ap- I garments, ability to control bacteria on the fabric, and

high degree of adsorption of the compound onto the surface of the fabric.

It is another object to provide improved detergent compositions containing one or more members of the new class of compounds. Since all of the members of the new class of compounds can be mixed together in all proportions without disturbing their valuable characteristics, such mixtures can be employed in detergent compositions.

More especially, the novel compounds of this invention are identified as p-alkyl or p-alkylphenyl sulfonylphenols having the following general formula wherein R represents a primary or secondary branched or straight chain aliphatic radical, containing from about to 18 carbon atoms, or a p-alkylphenyl group containing from about l0'to 18 carbon atoms in the alkyl substituent, and M is hydrogen or an alkali metal such as sodium or potassium.

These compounds constitute heretofore unknown compounds possessing a unique blend of physical properties which make them very useful and valuable compounds. Thus, the componds of this invention have been discovered characteristically to possess detergent activity, combined with bacteriostatic activity against both gram-positive andv gram-negative microorganisms. Moreover, it was discovered that these compounds exhibit a high de- This property enhances the bacteriostatic property since it increases the efliciency of bacterial control on the fabric. Yet further the compounds described herein exhibit good stability when exposed to light for prolonged periods. This offers good shelf life and greater flexibility in commercial applications of these new compounds.

Compounds offering the above unique blend of prop- "ice erties are fairly difiicult to prepare. This difliculty is due in part to the fact that the strongly electron withdrawing characteristics of the sulfonyl radical causes the failure of many of the more standard methods for bringing about the structural changes leading up to the preparation of the new compounds. This is especially true in certain steps more than in others. For example, in the last step of a preferred procedure detailed below, a number of commonly useful dealkylating reagents fail to react with the phenyl-methyl ether, because of the unusual strengthening of the carbon-oxygen bond by the p-substituted sulfonyl group. Out of the many dealkylating agents which were tried in this process, only anhydrous pyridine hydrochloride was found to work satisfactorily.

The particularly desirable compounds for realizing the benefits described and claimed are those of the general where R is either a primary or secondary, branched or straight chain alkyl group containing 10 to 14 carbon atoms and M is sodium or hydrogen. The most preferred compound contains a primary straight chain dodecyl radical and sodium and is technically named the sodium salt of p-dodecylsulfonylphenol.

Examples of the novel p-primary straight chain alkylsulfonylphenol compounds of this invention are: p-decylsulfonylphenol, p-dodecylsulfonylphenol, p-tetradecylsulfonylphenol, p-hexadecylsulfonylphenol, p-octadecylsulfonylpnenol. Examples of p-secondary straight chain alkylsulfonylphenol compounds of this invention are: p-(Z-dodecylsulfonyl) phenol and p-(2-octadecylsulfonyl) phenol. Examples of primary and secondary branched chain compounds are: p-(2-diethyl)-hexyl sulfonylphenol, p-(2-diethyl-4-methyl)-pentylsulfonylphenol. These compounds can be readily neutralized to sodium and potassium salt forms by reacting them with suitably alkaline reagents such as sodium hydroxide and potassium hydroxide. The neutralized alkali metal salt form is generally preferred for employment in the hereafter described detergent and laundry formulations.

The alkylphenyl radicals contemplated in the novel p-alkylphenylsulfonylphenol compounds of this invention are those in which the carbon content of the aliphatic substituent is a primary or secondary straight or branched chain alkyl containing from 10 to 18 carbon atoms. Such radicals are: decylphenyl, dodecylphenyl, tetradecylphenyl, hexadecylphenyl, ocbadecylpheny-l and branched chain isomers of these radicals, such as 2-dodecylphenyl, 3-dodecylphenyl, (2-diethyl-4-methyl) pentylphenyl and (Z-diethyl) -hexylphenyl.

The methods of preparing the compounds of the invention generally comprise the following sequence of steps The method just described may be more readily understood by a review of the following reaction flow diagram 3 equations which relate to a preferred method. phaSis, the equations have not been balanced.)

(For em- SOzCI(OH) Chlorosull'onatlon I Reduction 0 H; C H;

I SO zNa dOzR Alkylatlon Demethylation The following example will illustrate the foregoing method of preparing the novel compounds but it is merely intended to illustrate the invention and not in any manner define limits thereof.

EXAMPLE I Rara-dodecylsulfo-nyl phenol C H SO C H OH Step 1.--In a nitrogen swept 5 liter 3-necked flask, fitted with a mechanical stirrer, a thermometer, and a 500 ml. addition funnel protected with a CaCl drying tube, were placed 462 g. (4.28 moles) of methoxybenzene (anisole) and 1600 ml. of chloroform. The solution was stirred and cooled in an ice-salt bath to -7 C., and 1000 g. (8.56 moles) of chlorosulfonic acid were added dropwu'se', keeping the reaction temperature below 0 C. At the end of the addition, the ice bath was removed and the reaction mixture was stirred at room temperature for an additional 40 minutes, after which it was poured into 2 liters of cracked ice with stirring. The chloroform layer was separated and washed four times with 500 ml. portions of ice water and then dried over anhydrous MgSO The mixture was filtered and the solvent evaporated at atmospheric pressure. The productwas distilled under vacuum, B.P. 114-120 C. at 0.45 mm., to give 518.7 g'. (58.4%) of colorless crystals of p-methoxyphenylsulfonyl chloride.

Step 2.The p-methoxyphenylsulfonyl chloride was reduced with zinc in an alkaline medium as follows. Five liters of water were heated to 80 C. with live steam in a litertank, fitted with a stirrer, a thermometer, and a trap for the steam line. Zinc dust (516.7 g., 7.90 g. atom) was added to the vigorously stirred water, and 518 g. (2.498 moles) of p-methoxyphenylsulfonyl chloride from step 1 were added over minutes maintaining the temperature at 80-85 C. Stirring was continued for 10 minutes, then the temperature was raised to 90 C., and 500 ml. of 6 N NaOH were added. Sodium carbonate (400 g.) was then added cautiously, keeping the temperature at 90 (pH 10-11). The hot mixture was filtered through a Buchner funnel and the filter cake was slurried in 750 ml. of hot distilled water and filtered. The combined filtrates were placed in evaporating dishes and evaporated overnight on the steam bath to a low volume. After cooling to room temperature, the crystals were filtered. After air drying, the material was broken up and divided among three 3 liter beakers. The beakers were filled with alcohol and heated on the steam bath for 4 hours. The insoluble material was filtered out and the filtrates were cooled in the refrigerator for about 5 hours. The crystals were filtered out and washed with ice cold ethanol. The product consisted of 124.3 g. (25.6%) of sodium p-methoxyphenylsulfinate.

Step 3.-Sodium p-methoxyp'henylsulfinate (120.0 g., 0.618 mole) was put in a 2 liter flask equipped with an air condenser. n-Dodecyl bromide (182.0 g., 0.618 mole) was added to the flask, followed by 1200 ml. of dimethylforrnamide. The mixture was heated to reflux for 21 hours, and then distilled under reduced pressure. When bumping became too vigorous, concentration was continued on a Rinco evaporator, using an oil bath at 90- 110 C. The warm residue was allowed to solidify in an evaporating dish and was then broken up and extracted overnight in a Soxhlet thimble with 1 liter of acetone. The acetone extract was evaporated on the steam bath to give 200 g. (99.7%) of dodecyl p-metlhoxyphenylsulfone.

Step 4.T-he dodecyl p-methoxyphenylsulfone was demethylated by heating with anhydrous pyridine hydrochloride. Pyridine hydrochloride (200 g., 1.730 moles) was added to 200 g. (0.616 mole) of dodecyl p-methoxyphenylsulfone from step 3 in an N flushed 1 liter flask fitted with a reflux condenser protected by a CaCl tube. The mixture was heated in a. silicone bath at 210 C. for 12 hours. After cooling, the dark brown gelatinous mixture was transferred to a 6 liter separatory funnel with 4 liters of distilled water. The mixture was extracted with five 1 liter portions of diethyl ether. The ether solution was extracted with 3 liters of 0.29 molar NaOH solution divided into 5 portions. The aqueous alkaline extract was acidified with HCl (100 ml. conc. HCl diluted with 100 ml. :of distilled water) to pH 2 with continuous stirring. The acidic extract was extracted 6 times with 500 ml. portions of diethyl ether. The ether extracts were combined and dried over MgSO After filtering, fresh MgSO was added for further drying. The ether extract was again filtered and the solvent distilled oil under reduced pressure to give 130.5 g. (64.9%) of crude product. The crude product was recrystallized twice from a mixture of diethyl other (125 ml.) and petroleum ether (300 ml.) by cooling in an ice bath. 'llhe precipitate was filtered by suction and washed 3 times with cold diethyl ether (50 ml.) plus petroleum ether (300 ml.). The melting point of the recrystallized p-dodecylsulfonylphenol (93.1 g., 46.3%) was 59.4-6,0.0 C. Anal. for C13H30S03 S, 0211C. found In the foregoing example the starting material was methoxybenzene (anisole), C H OCH a phenyl-methyl ether that boils at 154 C. and which is insoluble in water, but soluble in chloroform, ether and hexane. When methoxybenzene is the starting material it is important to keep the reaction temperature in the chlorosulfonating step below about 10 C. and preferably at or below 0 C. in order to moderate the reaction and-to obtain the maximum yield of p-methoxyphenylsulfonyl chloride. Temperatures on the order of 20. C. to about 10 C. can be employed, witha preferred range being from -10 C. to about 0 C.

In place of methoxybenzene as a starting material, comparable results are obtained by using another O-substituted phenol, e.g. ethoxybenzene (phenetole),

Actually, any lower alkylphenyl ether can be used in which the alkyl radical contains from 1 to about 6 carbon atoms. The temperature range previously recited in connection with methoxybenzene is applicable to any of the additional alkylphenyl ethers.

The initial chlorosulfonation reaction proceeds well when the reactants are employed in the preferred ratio of one mole of the ether to two moles of chlorosulfonic acid.

medium drops too low, a problem arises in that excessive reduction of sulfinic acid salt will occur and the yield of the desired compound will be diminished. The appropriate alkaline medium may be obtained by using any basic materials such as sodium hydroxide, potassium hydroxide, sodium carbonate, or other well known basic materials. The preferred temperatures are in the range of 80 to 95 C.

In place of the n-dodecyl bromide used in the example, other sutficiently reactive high molecular weight organic halides can be used. For instance, primary or secondary straight or branched chain C to C alkyl halides are sufficiently reactive .and can be used with equally good results. For instance, decylbromide produces as the end product p-decylsulfonylphenol, tetradecylbromide produces p-tetradecylsulfonylphenol, and hexadecylbromide and octadecylbromide produce corresponding compounds. Alkyl bromides are the preferred halides but chlorides and iodides can also be used. Secondary alkyl halides which are contemplated are decyl-2-bromide, dodecyl-3- bromide and tetradecyl-2-bromide.

Alkylphenyl halides such as p-decylphenylchloride, pdode'cylphenylbromide, p-tetradecylphenylbromide, phexadecylphenylbromide and p-octadecylphenylbromide also produce good results and form the corresponding p-alkylphenylsulfonylphenols.

The temperature required for this alkylation reaction is between about 70 C. to about 130 C. and a preferred range is about 80 C. to 120 C.

The high boiling point solvent essential for this alkylation step can be dimethylformamide as in the example. In place of the dimethyl formamide, satisfactory results can be obtained with dimethylsulfoxide and dimethylacetamide.

The final demethylating step was found to present un'- usually difficult problems. Only anhydrous pyridine hydrochloride was capable of dealkylating the lower alkyl ether substituent while other conventional dealkylating agents failed to function in a satisfactory manner. Pyridine hydrochloride is a commerically available material, but in order to obtain satisfactory results the commercial material should be rendered anhydrous before use. The salt should be prepared directly from pyridine under conditions that alternatively allow its isolation in an anhydrous condition.

EXAMPLE II resentative member of the novel class and performing a standardized detergency test.

Naturally soiled swatches of desized print cloth were washed for ten minutes in an aqueous solution of a detergent to be evaluated. A miniature machine (Tergotometer) having normal reciprocating agitation was used. The cleansing composition contained 20% synthetic organic detergent surfactant in this instance sodium p-dodecylsulfonylphenol, 50% sodium tripolyphosphate, and 30% sodium sulfate. The composition was used at a level of 0.1% concentration. Water of 7 grains per gallon hardness at a temperature of 140 F. was used. The pH of the solution was 10.0

After washing, rinsing, and drying, the amount of lipid soil remaining on the washed swatch was determined by extraction with organic solvent. By comparison with similar determinations of the amount of lipid soil in similarly soiled unwashed swatches, the percent soil removal by the washing treatment can be found.

A relative measure of detergency efliciency was determined by repeating the above test procedure with a similar standardized cleansing composition in which the sodium p-dodecylsulfonylphenol was replaced in turn by dodecylbenzenesulfonate, sodium p-tetradecylsulfonylphenol and sodium p-hexadecylsulfonylphenol. The dodecylbenzenesulfonate was the sodium salt of sulfonated alkylbenzene in which the alkyl radicals range from about 9 to about 15 carbon atoms and average about 12 carbon atoms. The dodecyl radical was derived from a propylene' polymer, predominantly tetrapolypropylene.

A comparison of the results of the data so obtained established that the long chain, high molecular weight sulfonylphenol compounds of this invention were fairly comparable to dodecylbenzenesulfonate as a detergent compound. Similarly favorable results can be obtained by using the p-alkylphenyl-sulfonylphenol derivatives of this invention.

Short chain p-alkylsulfonylphenol compounds as a broad class of compounds have previously been synthesized. It Was surprising to discover, however, that the particular C to C p-alkyland p-alkylphenyl-sulfonylphenol compounds of this invention possess the highly desirable properties for use as organic detergents as eX- emplified by the preceding example, whereas the previously known short chain p-alkyl-sulfonylphenol compounds did not possess cleaning power.

As mentioned earlier, the members of this new class of compounds have been discovered to also possess bacteriostatic properties. This bacteriostatic activity was discovered by conducting Standard Tube Dilution Tests. Such tests are in vitro and consist essentially of preparing test tubes of standardized broth medium containing serial dilutions of a compound being tested, inoculating each tube with a preselected microorganism and, after an incubation period, calculating the growth of bacteria in each.

The broth medium employed in these assay tests was an FDA phenol coefficient test nutrient broth. Stock solutions of the test product were then prepared in sterile distilled water. Serial dilutions were then prepared of the test stock solution and then placed into the contact tubes containing the nutrient broth.

The contact tubes were then inoculated with bacterial organisms prepared in the following manner. A washed 24 hour broth culture of gram-positive Staphylococcus aureus ATCC 6538 was standardized to a predetermined turbidity, by dilution with sterile nutrient broth, to contain about 500,000,000 organisms per milliliter. Onetenth milliliter quantities of standardized inoculum were added to each previously prepared contact tube. Samples were similarly prepared for a representative gramnegative organism, Escherichia coli ATCC 10536.

Four contact tubes were thusly prepared for each inoculating organism at each serial dilution tested, of which three were inoculated and one was retained as an uninoculated control. p

The inoculated tubes are shaken thoroughly, allowed to stand for 10 minutes for air bubbles to rise, then read for a zero-hour turbidity value using a Coleman Junior Model 6A spectrometer set at a Wave length of 610 millimicrons.

After 24 hours of incubation at 37 C., the tubes are again shaken, allowed to stand for ten minutes, and then read to obtain 24 hour turbidity values. Differences in turbidity values are used as a measure of growth of the bacteria in the contact tubes. In this manner there was determined the minimum effective concentration of the antibacterial which prevents growth of the organism after incubation. This concentration (parts per million of bacteriostatic agent) is called the bacteriostatic breakpoint. (See Table I.)

In order to allow for a comparison of the relative bacteriostatio effectiveness of the novel p-alkylsulfonylphenol compounds, similar in vitro tests were run with the same surfactant compound that was used in the cleaning evaluations, namely dodecylbenzenesulfonate, referred to also as ABS. As before indicated, the ABS employed was the sodium salt of the sulfonic acid derived from the condensation product of benzene and propylenes having from 9 to about 15 carbon atoms and averaging 12 carbon atoms. Compared with other common anionic or nonionic detergents, ABS is regarded as having relatively fair bacteriostatic effectiveness. Accordingly, compounds which evidence substantially greater antibacterial effectiveness than dodecylbenzenesulfonate are considered in the art to be useful detergent bacteriostats and as such are always in demand for manifold useful purposes.

The results of the comparative in vitro tests described above are tabulated in Table I.

TABLE I Breakpoints (parts per million) The compounds of this invention are useful, per se, as detergent and surface active agents or they can be used conjointly with other materials to form detergent compositions, as for example, liquid, tablet or granular compositions. Such detergent compositions can contain the p-alkyland p-alkylphenylsulfonylphenol compounds of the present invention and water-soluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts or mixtures thereof in a ratio of the sulfonylphenol to builder salt of about 4:1 to about 1:20. A preferred ratio is 2:1 to 1:10. Builders are hereinafter more fully described.

Water-soluble inorganic alkaline builder salts used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand di-orthophosphate and potassium bicarbonate.

Examples of organic alkaline sequestrant builder salts used alone or in admixture are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium N-(2-hydroxyethyl)-nitrilodiacetates, Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see US. Patent 2,739,942).

Granular detergent compositions offering each of the foregoing described properties preferably contain about 5% to about 50% of a sulfonylphenol compound or mix- Anionic organic detergents which can be used in the compositions of this invention if desired include both the soap and non-soap detergents. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Parlow, i.e., sodium or potassium tallow and coconut soap. Examples of anionic organic non-soap detergents are:

alkyl glyceryl ether sulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethionates; acyl N-methyl taurides; alkylbenzenesulfonates; alkyl phenol polyethenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain 10 to 20 carbon atoms. They are used in the form of water-soluble salts, the sodium, potassium, ammonium, and alkylolammonium salts, for example. Specific examples are: sodium lauryl sulfate; potassium N-methyl lauryl' tauride; dodecylbenzene sulfonate.

The examples of nonionic organic detergents which can be used in the compositions of this invention if desired are: polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 1-2 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is pres- Another unexpected property of these new compounds which makes more valuable the foregoing bacteriostatic properties is that the new compounds arehighly adsorbent on cloth fabrics. The high substantivity of the new compounds towards fabrics washed with detergent compositions containing such new compounds enhances the effect which is obtained through bacteriostatic behavior of the compounds! The detergent compositions of this invention can contain any of the usual adjuvants, diluents and additives, for example, ampholytic, cationic or zwitterionic detergents, perfumes, antitarnishing agents, antiredeposition agents, bacteriostatic agents, dyes, fluorescers, suds builders, suds depressors and the like without detracting from the advantageous properties of the composition.

Cleansing and detergent compositions prepared according to this invention which have found particular applicability in the majority of household laundering situations can contain from about 2% to 50% by weight of the p-alkyland p-alkylphenylsulfonylphenol compounds, 25% to by weight of sodium tripolyphosphate, 12% to 45% by weight of sodium sulfate, 0% to 15% by weight of sodium silicate and 0% to about 40% by weight of water.

The following examples are presented for illustrative purposes only.

An excellent granular detergent compositionwas .prepared having the following formula:

Percent Sodium salt of p-dodecylsulfonylphenol 17.5 Sodium sulfate 23.0

Sodium tripolyphosphate 50.0 Sodium silicate 1 6.0

Water 3.5

A water solution containing from 0.15% to 0.45% concentration of the above formula provides very good cleaning results in both laundering and dishwashing situations.

The following are additional examples of suitable formulations containing compounds of the present invention.

9 Granular detergent Percent Sodium salt of p-dodecylsulfonylphenol Sodium dodecylbenzenesulfonate (the dodecyl group being derived from tetr-apropylene) 10 Sodium tripolyphosphate 50 Sodium sulfate 30 Granular detergent Sodium salt of p-tetradecylsulfonylphenol 10 Condensation product of one mole of nonyl phenol and nine moles of ethylene oxide 10 Sodium pyrophosphate 50 Sodium carbonate 3 Trisodium phosphate 3 Sodium sulfate 24 Liquid detergent Potassium salt of p-dodecylsulfonylphenol 6 Sodium dodecylbenzenesulfonate 6 Potassium pyrophosphate Potassium toluene sulfonate 8 Sodium silicate 3.8 Carboxymethyl hydroxyethyl cellulose 0.3 Water Balance In addition to being incorporated in laundering and dishwashing compositions to obtain the advantages discussed above, the eompounds of this invention can be used as ingredients in cleansing creams or similar cosmetic preparations where the antiseptic properties of the new compounds can be utilized. 1

The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be so limited since variations and modifications thereof I will be obvious to those skilled in the ant, all of which are within the spirit and scope of this invention.

What is claimed is:

l. A cleansing and detergent composition consisting essentially of (a) a detergent compound having the formula RS(O) C H OM, wherein R is a p-a lkyllphenyl radical containing from 10 to 18 carbon atoms in the alkyl substituent, and wherein M is selected from the group consisting of hydrogen and an alkali metal and (b) a builder selected from the group consisting of watersoluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts, and mixtures thereof in a ratio of the detergent compound to the builder of about 4:1 to about 1:20.

2. The cleansing and detergent composition of claim 1 wherein the detergent compound is the sodium salt of p-dodecylsulfonylphenol and the builder is sodium tripolyphosphate.

3. The cleansing and detergent composition of claim 1 in which the ratio of detergent to builder is 2:1 to 1:10.

References Cited by the Examiner UNITED STATES PATENTS 2,010,754 8/1935 Felix et al 260-607 2,017,004 10/ 1935 Kirstahler et a1 260-607 2,787,595 4/1957 Webb 252-133 3,151,084 9/ 1964- Schiltz et a1. 2521-38 XR References Cited by the Applicant UNITED STATES PATENTS 2,990,375 6/1961 Steinhauer et al. 3,000,831 9/ 1961 Tuvell.

FOREIGN PATENTS 597,099 1/ 1948 Great Britain.

ALBERT T. MEYERS, Primary Examiner. 

1. A CLEANING AND DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF (A) A DETERGENT COMPOUND HAVING THE FORMULA RS(O)2C6H5OM, WHEREIN R IS A P-ALKYLPHENYL RADICAL CONTAINING FROM 10 TO 18 CARBON ATOMS IN THE ALKYL SUBSTITUENT, AND WHEREIN M IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND AN ALKALI METAL AND (B) A BUILDER SELECTED FROM THE GROUP CONSISTING OF WATERSOLUBLE INORGANIC ALKALINE BUILDER SALTS, WATER-SOLUBLE ORGANIC ALKALINE SEQUESTRANT BUILDER SALTS, AND MIXTURE THEREOF IN A RATIO OF THE DETERGENT COMPOUND TO THE BUILDER OF ABOUT 4:1 TO ABOUT 1:20. 